Process of producing keto compounds.



rinrrnn s rains PATENT @FFXGEQ GEORG MERLING, 0F ELBERFELD, AND HUGO KUHEJEEL, 0F LEVERKUSEN, NEAR COLOGNE, GERMANY, ASSIGNORS TO FARIBENFAERIKEN VORM. FRIEDR. BAYER & (30., 0F ELBERFELD, GERMANY, A CORPORATIQN.GF GERMANY.

PROCESS OF PRODUCING KE'IO COMPOUNDS.

No Drawing.

Specification of .Letters lPatent. Application filed October a, 1912. Serial no. renew;

Fatented Aug. 119, 1913.

which have proved to be valuable intermediate products for the manufacture of erythrene and its homologues. The process for their production consists in treatingacetone and its homologues with a dimethylamino-methane compound, and more pariicularly with dimethylaminotixymethane or tetramethyldiaminomethane either with or without condensing agents, such. as caustlc alkalis, alkali carbonates and bicarbonates, alkaline earths, aluminium hydrate}, sodium phosphate, organic bases and salts. The condensation proceeds, although slowly, even at ordinary temperature and without condensing agents and the presence or absence of water or of-other solvents doesnot injuriousl interfere with the reaction. Heatmg an condensing agents accelerate the reaction. 'Dimethylammoiixymethane and tetramethyldiaminomethane can be used as such or as mixtures of formaldehyde and dimethylamin solutions in the proper molecular proportions or in the latter case also in statu nasoemlz'. e. 9. according to the following equations:

(R hydrogen or alkyl). Besides these products ketodiamins of the formula at-morn are obtained for instance by the two-fold introduction of the residue These reactions proceed diamins can be separated from the ketomonoamin's by fractional distillation.

In order to illustrate thenew process more fully the following examples are given, the parts being by weight:

Example 1: Production ofbeta-acetylpropyldlmethylamin and beta-beta-acetylmethyltrimethylenetetramethyldiamin /CH2.N.(CH1)2 from dimethylaminooxymethane and methylethylketone.

(a) 2000 parts of methylethylketone, 750

parts of dimethylaminooxy-methane among-morn):

(see Henry, Bull. Acad. Royale dc Belgz'que, vol. 28, 1894, p. 366), 1000 parts of water and 300 parts of baryta water saturated at ordinary temperature are heated in an autoclave to 40 C. until a test rtion after acidulation with acetic acid, is not any more rendered turbid by a solution of anilin acetate which requires about 3 to 4 days. The baryta is then precipitated fromthe clear brown solution by carbonic acid or alkaline bicarbonate, filtered off and the excess of the methyl-cthylketone and the ketobases prepared therefrom are precipitated from the filtrate by means of carbonate of potash and dried after separation from the aqueous solution with carbonate of potash. The excess of methylethylketone is now distilled ofl, advantageously under somewhat reduced pressure in an apparatus suitable for fractional distillation and the remaining oil is distilled in 'vacuo. The crude mixture of the bases distils over between 50 and 100 C. at a pressure of 18 mm. as a colorless oil, while a small quantity (20-30 parts) of a dark syrupy residue remains. The crude bases can be easily separated by repeated fractional distillations in oacuo into beta-acetyl-propyldimethylamin CH -CO-CH.(CH;)-CH -N.(CH)2 and beta-beta-acetylmethyltrimethylenetetrame'thyldiamin The former is a colorless thin oil of a 233519. The yield amounts to nearly 80 per cent. of the theory. The beta-betaacetylmethyltr i m e t h y l e 11 et e tramethyldiamin, which is produced in a small quantity, is a colorless, thick, almost odorless oil boiling at 110-112 C. (18 mm.). The production of beta-beta-acetylmethyltrimethylenetetramethyldiamin can be prevented by reducing the quantity of the baryta water to 20-100 parts but otherwise under the same conditions as above described. The completion of the reaction requlres 111 this case nearly a fortnight.

(b) 765 parts of aqueous 'dimethylamm solution (58.7 7 per cent.) are added to a mixture which has to be stirred, of 2500 parts of methylethylketone with 7 50 parts of aqueous formaldehyde (40 per cent). The temperature gradually rises to 35 C; After standing for about 25 days at ordinary temperature the pungent smell of dimethylamin-oxymethane has disappeared and the finished. The light red solution.

reaction is is worked up in the same manner as described in the preceding example, the yield being about 600 parts of beta-acetylropyldimethylamin and 250 parts 0 betabeta acetylmethyltrimethylenetetramethyldiamin. L

Example 2: Production of beta-acetylpropyldlmethylamin and beta-beta-acetylmethyltrimethylenetetramethyld1amin from tetramethyldiaminomethane and methyleth lketone. 7 50 parts of aqueous formaldehy e (40 per cent.) are gradually dropped into 1350 parts of an aqueous dimethylamin solution (58.77 per cent.) care being taken to stir well and cool during this operation and 2500 parts of methylethylketone and 100 parts of caustic soda lye (1 per cent.) are added to the solution of tetramethyldiaminomethane thus obtained. After this solution has been heated to 30 C. for about 20 days the pungent smell of tetramethyldiaminomethane has disappeared. The light red solution is saturated with carbonic acid or bicarbonate is added to it, the bases and the excess of methylethylketone are separated and dried with potash. The further working up of the crude mixture is then carried out in. the manner as described in the preceding examples. In this way about 700 parts of beta-acetylpropyldimethlyamin' and 100 parts of beta-beta-acetylmethyL- trimethylenetetramethyldiamin are obtained. The-same products but with a considerably smaller yield are obtained by boiling under a reflux condenser for 4 days equal molecules of ethylmethylketone and pure tetramethyldiaminomethane of the boiling point 85.

Example 3: Production of beta-acetylethyldimethylamin" cm-co-om-csr-awm and beta acetyl'trimethyleneetetramethyldlamin: CH:.N.(CH3):

CH1,N.(CH3):

from dimethylaminotixymethane and acetone. 765 parts of an aqueous dimethylamin solution (58.77 per cent.) are adually dropped into 750 parts of aqueous ormaldehyde (40 per cent.) which-has to be well stirred and cooled andv the solution of dimethylaminooxymethane thus obtained is mlxed with 2000 parts of acetone 500 parts of sodium lye (0.3 per cent.) I The temperature of the mixture gradually rises on standing from 10-to 30 C. After 3 to 4 days standing at ordinary tem erature the reaction is complete. The ree alkali'is removed from the brown solution by saturation with carbonic acid or by addition of bicarbonate and the oil is separated from the aqueous solution by potash and dried over potash. The excess of acetone is removed by distillation. brown oil, is distilled in cacao and the fraction from 4594 C. (19-20 mm.) a colorless oil (800 parts) is collected. The mixture thus obtained consists of about 33 per cent.

The residue, a

of beta-acetylethyldimethylamin and of 67 l per cent. of beta.-acetyltrimethylenetetramethyldiamin. The former base is identical with the ketobase from dimethylamin and methyleneacetone (described in German Letters Patent No. 233519). It is a colorless thin liquid oil having an intense smell and boils at 5758 C. (18 mm.). The beta-acetyltrimethylenetetramethyldiamin is a thick colorless almost odorless oil boiling at 9698 O. (16 m 7 1 'Exam 1e 4 Production of beta-acetylethyldimethy amin and beta-acetyltrimethylenetetramethyldiamin from tetramethyldiaminomethane and acetone. 750 parts of aqueous formaldehyde (40 per cent.) are gradually dropped into 1530 parts of aqueous dimethylamin solution (58.77 per cent.) whichis being stirred and cooled and 2000 parts of acetone, 400 parts of baryta Water (saturated at ordinary tempera-' amino substituted keto-compoun Lemons and ketodiamin obtained according to Example 3) 80 per cent. of a beta-acetylethyldimethylamin and 20 per cent. of beta-acetyltrimethylenetetramethyldiamin.

We claim 1. The process of producing a pol methylwhich comprises reacting on a ketone with a dimethylaminomethanc compound.

2. The process of producing a dimethylamino substituted ketone which comprises reacting on a ketone with dimethylaminooxymethane.

3. The process of producing a polymethylamino substituted keto-compound which comprises reacting on a ketone with a dimethylaminomethane compound with the addition of a condensing agent.

4. The process of producing a dimethylamino substituted keto-compound which comprises reacting on a ketone w1th d1- methylaminooxymethane with the addition of a condensing agent.

5. The process of producing a pol methylamino substituted keto-compoun which comprises reacting on a ketone with a dimethylaminomethane compound with the addition of an inorganic base as a. condensing agent.

6. The process of producing a polymethylamino substituted ketone which comprises reacting on a ketone with dimethylaminooxymethane with the addition of an inorganic base as a condenslng agent.

7. The process of producing keto compounds containing the radical or nucleus a R-C0- -d)-CHsN ZHa(R'-alkyl) which comprises treating a ketone with a dimethylaminonmethane compound.

8. The process of produclng keto-compounds containing the radical or nucleus on, RC0(liCHaN CH,(R-alkyl) which comprises treating a ketone with a dimethylaminomethane compound with the addition of a condensing agent.

9. The process of producing keto-compounds containing the nucleus containing-the radical:

which comprises treating a methyl ketone with a 'dimethylaminomethane compound.

10. The process of producing keto-compounds containing the nucleus which comprises treating a methyl ketone with a dimethylaminomethane compound with the addition of an inorganic base as a condensing agent.

11. The process of producing keto compounds containing the radical or nucleus (R=alkyl) which comprises treating a ketone with dimethylaminooxymethane with the addition of a condensing agent.

13. Process of producing-keto compounds containing the radical:

which process comprises treating a ketone with dimethylaminooxymethanc and then isolatin the keto compound produced, substantial y as described.

14.. Process of producing keto compounds l 4 cu CHu-GO-C-CHr-N I CH3 which process comprises treating a ketone with dimethylaminooxymethane with the addition of a condensing agent and then isolating the keto-compound produced, substantially as described.

In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

caone MERLING. HUGO actuate.

[n s.] [1a. 15.]

It is hereby certified that in Letters PatentiNo. 1,070,622 granted August 19, 1913, upon the application of George Merling, of Elberfeid, and Hugo Kohler, of Leverkusen, near Cologne, Germany, for an improvement in Processes of Producing Keto Compounds," an error appears in the printed specification requiring corre tion as follows: Page 1, lines 4H5, second part of formula, for

2 CH3 00 CHAR) (CHQZN 0H, ((3H,),

CH3 00 emu 0H, N(CH,)= NH (0H,)

1 CH (JO CH(R) CH N(CH,) NH (0H,; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

- Signed and sealed this 30th day of December, A. D2, 1913;

[SEAL] J. T. NEWTON,

Acting Commissioner of Patents.

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